CA2100562A1 - Process for producing 4h-3,1-benzoxazine-t-ones - Google Patents
Process for producing 4h-3,1-benzoxazine-t-onesInfo
- Publication number
- CA2100562A1 CA2100562A1 CA002100562A CA2100562A CA2100562A1 CA 2100562 A1 CA2100562 A1 CA 2100562A1 CA 002100562 A CA002100562 A CA 002100562A CA 2100562 A CA2100562 A CA 2100562A CA 2100562 A1 CA2100562 A1 CA 2100562A1
- Authority
- CA
- Canada
- Prior art keywords
- groups
- alkyl
- halogen
- reaction
- alkoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/20—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with hetero atoms directly attached in position 4
- C07D265/22—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Production of 4H-3,1-benzoxazine-4-ones of formula (I) in which:
R1 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, carboxyl, sulpho, nitro or halogen; R2 is C1-C20-alkyl, phenyl or phenylalkyl with 1 to 4 C atoms in the alkyl group, whereby a phenyl nucleus may be substituted by one or two C1-C4-alkyl groups, C1-C3-halogen alkyl groups, C1-C4-alkoxy groups, C1-C3-halogen alkoxy groups, C1-C4-alkyl mercapto groups, C1-C3-halogen alkyl mercapto groups, carboxyl groups, sulpho groups, C1-C4-alkyl sulphonyl groups, C1-C3-halogen alkyl sulphonyl groups, nitro groups or halogen atoms; and n is 1 or 2; by the reaction of isato acid anhydrides of formula (II) with acyl halides of formula (III) in which X is chlorine or bromine, by conducting the reaction at an outside temperature of 215 to 280 ·C and causing the reaction components (II and III) to react together for at least 4 hours at this temperature.
R1 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, carboxyl, sulpho, nitro or halogen; R2 is C1-C20-alkyl, phenyl or phenylalkyl with 1 to 4 C atoms in the alkyl group, whereby a phenyl nucleus may be substituted by one or two C1-C4-alkyl groups, C1-C3-halogen alkyl groups, C1-C4-alkoxy groups, C1-C3-halogen alkoxy groups, C1-C4-alkyl mercapto groups, C1-C3-halogen alkyl mercapto groups, carboxyl groups, sulpho groups, C1-C4-alkyl sulphonyl groups, C1-C3-halogen alkyl sulphonyl groups, nitro groups or halogen atoms; and n is 1 or 2; by the reaction of isato acid anhydrides of formula (II) with acyl halides of formula (III) in which X is chlorine or bromine, by conducting the reaction at an outside temperature of 215 to 280 ·C and causing the reaction components (II and III) to react together for at least 4 hours at this temperature.
Description
` . ., b . . . ~
:: BASIFAKTIE~o~SELLSC~AFT . ~ o.z oo50/421~15 2100.~62 Preparation of 4H-3,1-E3enzoxazin-4-ones The present invention relates to an improved process for ~h~ preparation of a 4H-3,1-b0nzoxazin-4~one of the general formula I below ~!
~ ` 5 (R1)n~ R2 O
in which R1 denotes hydrogen, C1-C~-alkyl, C1-C"-alkoxy, carboxyl, sulfo, nitro, or halogen, .~ R2 denotes phenyl, or phenylalkyl containing from 1 to 4 carbon atoms in the alkyl group, which phenyl nucleus, if present, may be substituted by ' 15 one or two C1-C4-alkyl groups, C1-C3-haloalkyl groups, C1-C4-alkoxy groups, C~-C3-haloalkoxy groups, C1-C4-alkylmercaptQgroups, C~-C3-haloalkylmercapto groups, carboxyl groups, suifo groups, C1-C4-~ alkylsulfonyl groups, C1-C3-haloalkylsulfonyl groups, nitro groups, or : halogen atoms, and ` -~' n is equal to 1 or 2, - by reacting an isatoic anhydride of the general formula ll below (~1)n~~
with an acyl halide of the general formula lll ' 30 0 X~R2 1 1 1 in which X denotes chlorine or bromine, ~ the amount of acyl halide used beiny from li.0 to 1.5 moles per mole of - isatoic anhydride 11.
-;
:
;~ "' 1 ",..";,..
~,i , . . .
:. .
"
"
BAsFAKT~ENG~sEL~sc~AFT 2 1 0 ~ :~ fi 2 oz oos~/42145 E.v.Meyer and Th.Bellmann describe, in J prakt. Chemie, Vol 30 (188~), pp. 484-487, and Vol. 33 (1886), pp. 18-31, a process for the preparation of "benzoyl anthranil" (2-phenyl-4H-3,1-benzoxazin-4-one) by heatiny unsubstitutad isatoic anhydrids (erroneously referred to as isatoic acid in said references) with excess benzoyl chloride to the boil or at 210C in a "closed tube". The reaction is describ~d as being incomplet0 ~"a large quantity of unchanged isatoic acid mix0d with bcnzoyl anthranil s0parates from the solutionn). Detailsd statements regarding the r~action time, batch size, stoichiometry of the starting materials, and yield ars not made.
DE-A 3,~14, 183 refers to a process for tha preparation of optionally substituted 2-phenyl-4H-3,1-benzoxazin-4-ones by reacting an appropriate anthranilic acid with an appropriate b0nzoyl halide in the presence of a base (acylation) followed by ring formation via dehydration ~cyclization).
~s DE-AS 2,556,590 describes a process for ths preparation of benzoxazines, especially 2-alkyl- or 2-aryl-4H-3,1-benzoxazin-4-ones, in which an isatoic anhydride is reacted with an acylating agent in the form of a carboxylic anhydride or acyl halide in the presence of an effective amount of a tertiary 20 amine.
Chemical Abstracts, Vo/. 99, page 621, 1983, No. 158,452c, discloses that 2-methyl-4H-3,1 -benzoxazin-4-one can be produced in a yield of 84 % by reacting isatoic anhydride with acetic anhydride.
, 25 However, the aforementioned processes are still unsatisfactory from an economic point of view sither because their yields are too IGW or because they involve complicated multi-stags procedures or require the use of expensive auxi~a~ chemicals.
It is an object of the present invsntion, therefors, to provide a simple, efficient, and sconomical process for the preparation of 4H-3,1-benzoxazin-4-ones 1.
~Y~
35 Accordingly, we have found the process defined above, wherein the reaction is carried out at an external temperature of from 215 to 280C and the reactants ll and lll are caused to rsact at thls tsmperature for at Isast 4 hours.
40 In a preferred ~mbodiment, the external temperature us~d for this reaction ranges from 220 to 250C. By 'sxternal tsmpsrature' we msan ths ;; 2 , ... .
. ~l BASFAKTIE~GES~LLSC~-AFT 2 1 ~ O ~ 6 2 o.i~,oo50/~121~5 temperature of the jacket surrounding the reaction vessel, more particularly the temperatur~ of the heating liquid contained ther~in ,..
.:
Idealiy, the internal temperature, ie th0 temperature of the reaction mixture s itself, and the external temperature should be identical, but in practice the u i internal temperature will be a few degrees lower than the externalternperature. Another point to be observed is that when an acyl halide lll is used which boils at a temperature below the range d0sigrlated for the ; '~ reaction within the scope of the present invention, the internal temperature ~, 1D during the initial stages of the reaction will be equal to the boiling point of l~l (eg 197C in the case of benzoyl chloride), but as the concentration of free acyl halide ll in the reaction mixture diminishes the internal t~mperature will rapidly rise toward the value of the select0d external temperature.
: .
The duration of reaction at a temperature in the range stated is at least 4 hours, after which time the degree of conversion is normally from 80 to 95 percent. However, more satisfactory results are obtained by allowing the reac~ion to continue for at least 5 hours, as the degree of conversion is then usually 95 percent or higher. Following a reaction ~irne of 6 hours the conversion is usually virtually quantitative.
The reaction is advantageously carried out under standard pressure conditions. It is not necessary to operate in a closed reaction vessel undar autogenous pressure or in an autoclave at an elevated pressure, which would in any case be undesirable for safety reasons on account of the fact that the reaction leads to the liberation of gases ~ hydrog~n chloride and carbon dioxide), which require removal.
For each mol~of~isatoic anhydride ll there will be used from 1.0 to 1.5 moles of acyl halide lll. The use of a larger excess of lll frequently prevents the reaction mixture from reaching the temperature required for achieving a rapid reaction, A particularly favorable amount of lll is from 1.0 to 1.3 moles and more particularly from 1.05 to 1.2 moles, per mole of ll.
The acyl halide lll may be acyl bromide (X=Br) or, mora preferably, acyl chloride (X=CI).
~ , j; il The radicals R1, which can be attached to the benzene nucleus of the heterocyclic system in the five, six, seven and/or eight position, may be hydrogen or yroups as listed below:
:,~
'.i'.~,.5 ''~' 3 ,, ;~), i -, "~ I , , ~;:
BAsFAKT,ENGEsEL~scHAFT 2 1 ~to f~l~ oz,ooso/~t2145 - C~-C4-alkyl such as methyl, ethyl, n-propyl, isopropyl, n~butyl, isobutyl, s-butyl, and t-butyl;
- C~-C4-alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s isobutoxy, s-butoxy, t-butoxy, and methylene-dioxy;
; ~'.~;!' - carboxyl, advantag~ously in th~ form of th~ fr~e acid;
- sulfo, advantageously in the form of the free acid;
,0 - nitro; and - halogen such as fluorin0, chlorine, and bromine.
The preferred values of R1 are methyl, methoxy, halo~en, and in particular hydrogen.
The nurnber (n) of radicals R1 is two or, preferably, one.
A suitable radical R2 in the two position of the benzoxazin-4-one system is:
- phenyl; and . ,j ` 2s - ph~nylalkyl containing from 1 to 4 carbon atoms in the alkyl moiaty, eg benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl.
If a phenyl nucleus is present in the radical R2, it may b~ substituted in the ortho, meta, or para position by two or, pref~rably, one of the following radicals: ~
C~-C4-alkyl such as methyl, ethy., n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl;
- C~-C3-haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, and trifluoromethyl;
- C~-C4-alkoxy such as msthoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, and methylene~dioxy;
;' ' - C~-C3-haloalkoxy such as difluoromethoxy, trifluoromethoxy, chlorodifluoro-methoxy, 1,1,2,2-tetrafluoroethoxy, and 1,1,2-trifluoro-2-chloroethoxy;
.; 4 , ;-,~ .
~ , BAsFAKTIENGEsELLscHAFT 2 1 ~ o.z ooso/42145 - C1-C4-alkylmercapto such as methylmercapto, ethylmercapto, n~propyl-mercapto, and n-butylmercapto;
- C1-C3-haloalkoxymercapto such as difluoromethylmercapto, trifluoromethyl-5 mercapto, chlorodifluoromethylmercapto, and 1,1,2,2-tetrafluoroethylmer-capto;
- carboxy, advantageously in th~ form of the free acid;
,0 - sulfo, advantageously in the form of the fre~ acid;
- C1-C4-alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, and n-butylsulfonyl;
- C1-C3-haloalkylsulfonyl such as chlorom0thylsulfonyl and trifluoromethyl-suHonyl;
- nitro; or 20 - halogen such as fluorine, chlorine, and bromine.
The preferred values of R2 are:
- unsubstituted phenyl, - phenyl substituted by C1-C4-alkyl, especkally methyl, phenyl substituted by C~-C3-haloalkyl, 30 - phenyl substituted by C~-C4-alkoxy, especially methoxy, - phenyl substituted by C~-C3-haloalkoxy, ~;~ - phenyl substituted by Cl-Cl-haloalkylmercapto, - phenyl substituted by C~-C4-alkylsulfonyl, especially methylsulfonyl, - phenyl substituted by C~-C3-haloalkylsulfonyl, 40 - phenyl substituted by nitro, and `; 5 , I , .
' . , BAs~AKTIEN~EsELLscHAFT 2 1 0 ~ ~ 6 2 o,z,ooso/42145 - phenyi substituted by halogen.
On completion of the raaction, the resulting cornpounds I can be purified by : conventional ri~ethods, for example by recrystallization or distillation, and/ar ,' ~ 5 can be shaped, if desired, by a conventional method such as yranulation ~; from the melt, before or after the purifying step.
The process of the invention produces 4H-3,1-benzoxazin-4~ones in a '~ simple and economical manner and to a high degree of efficiency, ie in high yields. No auxiliary substances of any kind such as solvsnts or catalysts are required. The reaction is virtually complete after a short tinne, which gives rise to a high space-time yield. In most cases, the purity of the product is - adequate, so that no further purification is necessary in a number of applications.
4H-3,1-benzoxazin-4-on0s (I) are variously important compounds. For example, they can be used in the fields of plant protection, pharmaceutics, ; ' detergent additives or UV-stabilizers. For instance, compounds I having halogen, methyl, or methoxy as R1 and halophenyl, haloalkylphenyl, 2~ haloalkoxaphenyl, haloalkylmercaptophenyl, or haloalkylsulfonylphenyl (C1-C3-alkyi in all cases) as R2 can be used as selective herbicides. Certain 2-;~ subs~ituted 4H-3,1-benzoxazin-4-ones are suitable for US9 as cold bleach ~, activators in detergent formulations.
;~
"'~ 25 Exa7npie .
Preparation of 2-phenyl-4H-3,1 -benzoxazin--4-one 163.1 g (1.0 mole) of isatoic anhydride and 154.7 g (1.1 moles) of benzoyl - chloride were reacted with stirring in a reaction v0ssel having a 3acket :'.';:' 30 temperature of 220-225C. Hydrogen chloride and carbon dioxide were givsn off. As the reaction proceeded, the internal temperature of the reaction mixture rose from 197C to 215C. The amount of gas liberated by the reaction formed the basis for calculating the conversion against reaction time:
, ..~ ";.
i.:,...
:.. ..
', ~ . 5~1 " :
:".~.. , .
"1 ~ ' .
,, BAsFAKTIENGEsELLscHAFT 2 1 a ~ ~ .J 2 o i.ooso/42145 Reaction time ~h] Conversion ~/OJ
i~ 3 72 s ~ g3 ; ` , 0 On completion of gas generation (after 6 hours), the resulting crude product was purifi~d by distillation at 160C/1mbar. There w~re obtained 227 g of . 2-phenyl-4H-3,1-benzoxazin-4-on0 (yield 94%) in the form of a colorl0ss ~ ~ oil which crystalliz0d on cooling.
; ' .
:~ .
~ .
; .
_ _ .. . .
;
.
: -. 7 ;i ,., .
, , '' ': . .
..
,
:: BASIFAKTIE~o~SELLSC~AFT . ~ o.z oo50/421~15 2100.~62 Preparation of 4H-3,1-E3enzoxazin-4-ones The present invention relates to an improved process for ~h~ preparation of a 4H-3,1-b0nzoxazin-4~one of the general formula I below ~!
~ ` 5 (R1)n~ R2 O
in which R1 denotes hydrogen, C1-C~-alkyl, C1-C"-alkoxy, carboxyl, sulfo, nitro, or halogen, .~ R2 denotes phenyl, or phenylalkyl containing from 1 to 4 carbon atoms in the alkyl group, which phenyl nucleus, if present, may be substituted by ' 15 one or two C1-C4-alkyl groups, C1-C3-haloalkyl groups, C1-C4-alkoxy groups, C~-C3-haloalkoxy groups, C1-C4-alkylmercaptQgroups, C~-C3-haloalkylmercapto groups, carboxyl groups, suifo groups, C1-C4-~ alkylsulfonyl groups, C1-C3-haloalkylsulfonyl groups, nitro groups, or : halogen atoms, and ` -~' n is equal to 1 or 2, - by reacting an isatoic anhydride of the general formula ll below (~1)n~~
with an acyl halide of the general formula lll ' 30 0 X~R2 1 1 1 in which X denotes chlorine or bromine, ~ the amount of acyl halide used beiny from li.0 to 1.5 moles per mole of - isatoic anhydride 11.
-;
:
;~ "' 1 ",..";,..
~,i , . . .
:. .
"
"
BAsFAKT~ENG~sEL~sc~AFT 2 1 0 ~ :~ fi 2 oz oos~/42145 E.v.Meyer and Th.Bellmann describe, in J prakt. Chemie, Vol 30 (188~), pp. 484-487, and Vol. 33 (1886), pp. 18-31, a process for the preparation of "benzoyl anthranil" (2-phenyl-4H-3,1-benzoxazin-4-one) by heatiny unsubstitutad isatoic anhydrids (erroneously referred to as isatoic acid in said references) with excess benzoyl chloride to the boil or at 210C in a "closed tube". The reaction is describ~d as being incomplet0 ~"a large quantity of unchanged isatoic acid mix0d with bcnzoyl anthranil s0parates from the solutionn). Detailsd statements regarding the r~action time, batch size, stoichiometry of the starting materials, and yield ars not made.
DE-A 3,~14, 183 refers to a process for tha preparation of optionally substituted 2-phenyl-4H-3,1-benzoxazin-4-ones by reacting an appropriate anthranilic acid with an appropriate b0nzoyl halide in the presence of a base (acylation) followed by ring formation via dehydration ~cyclization).
~s DE-AS 2,556,590 describes a process for ths preparation of benzoxazines, especially 2-alkyl- or 2-aryl-4H-3,1-benzoxazin-4-ones, in which an isatoic anhydride is reacted with an acylating agent in the form of a carboxylic anhydride or acyl halide in the presence of an effective amount of a tertiary 20 amine.
Chemical Abstracts, Vo/. 99, page 621, 1983, No. 158,452c, discloses that 2-methyl-4H-3,1 -benzoxazin-4-one can be produced in a yield of 84 % by reacting isatoic anhydride with acetic anhydride.
, 25 However, the aforementioned processes are still unsatisfactory from an economic point of view sither because their yields are too IGW or because they involve complicated multi-stags procedures or require the use of expensive auxi~a~ chemicals.
It is an object of the present invsntion, therefors, to provide a simple, efficient, and sconomical process for the preparation of 4H-3,1-benzoxazin-4-ones 1.
~Y~
35 Accordingly, we have found the process defined above, wherein the reaction is carried out at an external temperature of from 215 to 280C and the reactants ll and lll are caused to rsact at thls tsmperature for at Isast 4 hours.
40 In a preferred ~mbodiment, the external temperature us~d for this reaction ranges from 220 to 250C. By 'sxternal tsmpsrature' we msan ths ;; 2 , ... .
. ~l BASFAKTIE~GES~LLSC~-AFT 2 1 ~ O ~ 6 2 o.i~,oo50/~121~5 temperature of the jacket surrounding the reaction vessel, more particularly the temperatur~ of the heating liquid contained ther~in ,..
.:
Idealiy, the internal temperature, ie th0 temperature of the reaction mixture s itself, and the external temperature should be identical, but in practice the u i internal temperature will be a few degrees lower than the externalternperature. Another point to be observed is that when an acyl halide lll is used which boils at a temperature below the range d0sigrlated for the ; '~ reaction within the scope of the present invention, the internal temperature ~, 1D during the initial stages of the reaction will be equal to the boiling point of l~l (eg 197C in the case of benzoyl chloride), but as the concentration of free acyl halide ll in the reaction mixture diminishes the internal t~mperature will rapidly rise toward the value of the select0d external temperature.
: .
The duration of reaction at a temperature in the range stated is at least 4 hours, after which time the degree of conversion is normally from 80 to 95 percent. However, more satisfactory results are obtained by allowing the reac~ion to continue for at least 5 hours, as the degree of conversion is then usually 95 percent or higher. Following a reaction ~irne of 6 hours the conversion is usually virtually quantitative.
The reaction is advantageously carried out under standard pressure conditions. It is not necessary to operate in a closed reaction vessel undar autogenous pressure or in an autoclave at an elevated pressure, which would in any case be undesirable for safety reasons on account of the fact that the reaction leads to the liberation of gases ~ hydrog~n chloride and carbon dioxide), which require removal.
For each mol~of~isatoic anhydride ll there will be used from 1.0 to 1.5 moles of acyl halide lll. The use of a larger excess of lll frequently prevents the reaction mixture from reaching the temperature required for achieving a rapid reaction, A particularly favorable amount of lll is from 1.0 to 1.3 moles and more particularly from 1.05 to 1.2 moles, per mole of ll.
The acyl halide lll may be acyl bromide (X=Br) or, mora preferably, acyl chloride (X=CI).
~ , j; il The radicals R1, which can be attached to the benzene nucleus of the heterocyclic system in the five, six, seven and/or eight position, may be hydrogen or yroups as listed below:
:,~
'.i'.~,.5 ''~' 3 ,, ;~), i -, "~ I , , ~;:
BAsFAKT,ENGEsEL~scHAFT 2 1 ~to f~l~ oz,ooso/~t2145 - C~-C4-alkyl such as methyl, ethyl, n-propyl, isopropyl, n~butyl, isobutyl, s-butyl, and t-butyl;
- C~-C4-alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s isobutoxy, s-butoxy, t-butoxy, and methylene-dioxy;
; ~'.~;!' - carboxyl, advantag~ously in th~ form of th~ fr~e acid;
- sulfo, advantageously in the form of the free acid;
,0 - nitro; and - halogen such as fluorin0, chlorine, and bromine.
The preferred values of R1 are methyl, methoxy, halo~en, and in particular hydrogen.
The nurnber (n) of radicals R1 is two or, preferably, one.
A suitable radical R2 in the two position of the benzoxazin-4-one system is:
- phenyl; and . ,j ` 2s - ph~nylalkyl containing from 1 to 4 carbon atoms in the alkyl moiaty, eg benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl.
If a phenyl nucleus is present in the radical R2, it may b~ substituted in the ortho, meta, or para position by two or, pref~rably, one of the following radicals: ~
C~-C4-alkyl such as methyl, ethy., n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl;
- C~-C3-haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, and trifluoromethyl;
- C~-C4-alkoxy such as msthoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, and methylene~dioxy;
;' ' - C~-C3-haloalkoxy such as difluoromethoxy, trifluoromethoxy, chlorodifluoro-methoxy, 1,1,2,2-tetrafluoroethoxy, and 1,1,2-trifluoro-2-chloroethoxy;
.; 4 , ;-,~ .
~ , BAsFAKTIENGEsELLscHAFT 2 1 ~ o.z ooso/42145 - C1-C4-alkylmercapto such as methylmercapto, ethylmercapto, n~propyl-mercapto, and n-butylmercapto;
- C1-C3-haloalkoxymercapto such as difluoromethylmercapto, trifluoromethyl-5 mercapto, chlorodifluoromethylmercapto, and 1,1,2,2-tetrafluoroethylmer-capto;
- carboxy, advantageously in th~ form of the free acid;
,0 - sulfo, advantageously in the form of the fre~ acid;
- C1-C4-alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, and n-butylsulfonyl;
- C1-C3-haloalkylsulfonyl such as chlorom0thylsulfonyl and trifluoromethyl-suHonyl;
- nitro; or 20 - halogen such as fluorine, chlorine, and bromine.
The preferred values of R2 are:
- unsubstituted phenyl, - phenyl substituted by C1-C4-alkyl, especkally methyl, phenyl substituted by C~-C3-haloalkyl, 30 - phenyl substituted by C~-C4-alkoxy, especially methoxy, - phenyl substituted by C~-C3-haloalkoxy, ~;~ - phenyl substituted by Cl-Cl-haloalkylmercapto, - phenyl substituted by C~-C4-alkylsulfonyl, especially methylsulfonyl, - phenyl substituted by C~-C3-haloalkylsulfonyl, 40 - phenyl substituted by nitro, and `; 5 , I , .
' . , BAs~AKTIEN~EsELLscHAFT 2 1 0 ~ ~ 6 2 o,z,ooso/42145 - phenyi substituted by halogen.
On completion of the raaction, the resulting cornpounds I can be purified by : conventional ri~ethods, for example by recrystallization or distillation, and/ar ,' ~ 5 can be shaped, if desired, by a conventional method such as yranulation ~; from the melt, before or after the purifying step.
The process of the invention produces 4H-3,1-benzoxazin-4~ones in a '~ simple and economical manner and to a high degree of efficiency, ie in high yields. No auxiliary substances of any kind such as solvsnts or catalysts are required. The reaction is virtually complete after a short tinne, which gives rise to a high space-time yield. In most cases, the purity of the product is - adequate, so that no further purification is necessary in a number of applications.
4H-3,1-benzoxazin-4-on0s (I) are variously important compounds. For example, they can be used in the fields of plant protection, pharmaceutics, ; ' detergent additives or UV-stabilizers. For instance, compounds I having halogen, methyl, or methoxy as R1 and halophenyl, haloalkylphenyl, 2~ haloalkoxaphenyl, haloalkylmercaptophenyl, or haloalkylsulfonylphenyl (C1-C3-alkyi in all cases) as R2 can be used as selective herbicides. Certain 2-;~ subs~ituted 4H-3,1-benzoxazin-4-ones are suitable for US9 as cold bleach ~, activators in detergent formulations.
;~
"'~ 25 Exa7npie .
Preparation of 2-phenyl-4H-3,1 -benzoxazin--4-one 163.1 g (1.0 mole) of isatoic anhydride and 154.7 g (1.1 moles) of benzoyl - chloride were reacted with stirring in a reaction v0ssel having a 3acket :'.';:' 30 temperature of 220-225C. Hydrogen chloride and carbon dioxide were givsn off. As the reaction proceeded, the internal temperature of the reaction mixture rose from 197C to 215C. The amount of gas liberated by the reaction formed the basis for calculating the conversion against reaction time:
, ..~ ";.
i.:,...
:.. ..
', ~ . 5~1 " :
:".~.. , .
"1 ~ ' .
,, BAsFAKTIENGEsELLscHAFT 2 1 a ~ ~ .J 2 o i.ooso/42145 Reaction time ~h] Conversion ~/OJ
i~ 3 72 s ~ g3 ; ` , 0 On completion of gas generation (after 6 hours), the resulting crude product was purifi~d by distillation at 160C/1mbar. There w~re obtained 227 g of . 2-phenyl-4H-3,1-benzoxazin-4-on0 (yield 94%) in the form of a colorl0ss ~ ~ oil which crystalliz0d on cooling.
; ' .
:~ .
~ .
; .
_ _ .. . .
;
.
: -. 7 ;i ,., .
, , '' ': . .
..
,
Claims (2)
1. A process for the preparation of a 4H-3,1-benzoxazin-4-one of the general formula I below I
in which R1 denotes hydrogen, C1-C4-alkyl, C1-C4-alkoxy, carboxyl, sulfo, nitro, or halogen, R2 denotes phenyl, or phenylalkyl containing from 1 to 4 carbon atoms in the alkyl group, which phenyl nucleus, if present, may be substituted by one or two C1-C4-alkyl groups, C1-C3-haloalkyl groups, C1-C4-alkoxy groups, C1-C3-haloalkoxy groups, C1-C4-alkylmercapto groups, C1-C3-haloalkylmercapto groups, carboxyl groups, sulfo groups, C1-C4-alkylsulfonyl groups, C1-C3-haloalkylsulfonyl groups, nitro groups, or halogen atoms, and n is equal to 1 or 2, by reacting an isatoic anhydride of the general formula II below II
with an acyl halide of the general formula III
III
in which X denotes chlorine or bromine, the amount of acyl halide used being from 1.0 to 1.5 moles per mole of isatoic anhydride II, wherein the reaction is carried out at an external temperature of from 215°
to 280°C and the reactants II and III are caused to react at this temperature for at least 4 hours.
in which R1 denotes hydrogen, C1-C4-alkyl, C1-C4-alkoxy, carboxyl, sulfo, nitro, or halogen, R2 denotes phenyl, or phenylalkyl containing from 1 to 4 carbon atoms in the alkyl group, which phenyl nucleus, if present, may be substituted by one or two C1-C4-alkyl groups, C1-C3-haloalkyl groups, C1-C4-alkoxy groups, C1-C3-haloalkoxy groups, C1-C4-alkylmercapto groups, C1-C3-haloalkylmercapto groups, carboxyl groups, sulfo groups, C1-C4-alkylsulfonyl groups, C1-C3-haloalkylsulfonyl groups, nitro groups, or halogen atoms, and n is equal to 1 or 2, by reacting an isatoic anhydride of the general formula II below II
with an acyl halide of the general formula III
III
in which X denotes chlorine or bromine, the amount of acyl halide used being from 1.0 to 1.5 moles per mole of isatoic anhydride II, wherein the reaction is carried out at an external temperature of from 215°
to 280°C and the reactants II and III are caused to react at this temperature for at least 4 hours.
2. A process for the preparation of a 4H-3,1-benzoxazin-4-one (I) as set forth in claim 1, wherein the reaction is carried out at an external temperature of from 220° to 250°C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19914101380 DE4101380A1 (en) | 1991-01-18 | 1991-01-18 | PROCESS FOR THE PREPARATION OF 4H-3,1-BENZOXAZINE-4-ONEN |
| DEP4101380.8 | 1991-01-18 | ||
| PCT/EP1992/000025 WO1992012971A1 (en) | 1991-01-18 | 1992-01-08 | Process for producing 4h-3,1-benzoxazine-t-ones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2100562A1 true CA2100562A1 (en) | 1992-07-19 |
Family
ID=6423266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002100562A Abandoned CA2100562A1 (en) | 1991-01-18 | 1992-01-08 | Process for producing 4h-3,1-benzoxazine-t-ones |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0569377A1 (en) |
| JP (1) | JPH06504532A (en) |
| CA (1) | CA2100562A1 (en) |
| DE (1) | DE4101380A1 (en) |
| WO (1) | WO1992012971A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4134770A1 (en) * | 1991-10-22 | 1993-04-29 | Basf Ag | GRAINY BLEACH ACTIVATOR COMPOSITION |
| WO1993022300A1 (en) * | 1992-04-23 | 1993-11-11 | Bp Chemicals Limited | Process for the production of 2-phenyl-benzoxazin-4-one |
| WO1997048707A1 (en) * | 1996-06-20 | 1997-12-24 | Smithkline Beecham Plc | 4h-3,1-benzoxazin-4-one derivatives and analogs as antiviral agents |
| US6774232B2 (en) | 2001-10-22 | 2004-08-10 | Cytec Technology Corp. | Low color, low sodium benzoxazinone UV absorbers and process for making same |
| CN115043782B (en) * | 2022-06-01 | 2023-08-08 | 贵州省中国科学院天然产物化学重点实验室(贵州医科大学天然产物化学重点实验室) | 4H-3, 1-benzoxazine-4-one derivative and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3514183A1 (en) * | 1985-04-19 | 1986-10-23 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING SUBSTITUTED 2-PHENYL-4H-3,1-BENZOXAZINE-4-ONE |
-
1991
- 1991-01-18 DE DE19914101380 patent/DE4101380A1/en not_active Withdrawn
-
1992
- 1992-01-08 EP EP19920901610 patent/EP0569377A1/en not_active Withdrawn
- 1992-01-08 CA CA002100562A patent/CA2100562A1/en not_active Abandoned
- 1992-01-08 WO PCT/EP1992/000025 patent/WO1992012971A1/en not_active Application Discontinuation
- 1992-01-08 JP JP4502084A patent/JPH06504532A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE4101380A1 (en) | 1992-07-23 |
| WO1992012971A1 (en) | 1992-08-06 |
| JPH06504532A (en) | 1994-05-26 |
| EP0569377A1 (en) | 1993-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1081141B1 (en) | Method for producing 1,2-benzisothiazol-3-ones | |
| US3155678A (en) | Certain isothiazole compounds and their production | |
| US3822257A (en) | Production of 2,1,3-benzothiadiazin-4-one-2,2-dioxides | |
| CA2100562A1 (en) | Process for producing 4h-3,1-benzoxazine-t-ones | |
| EP1197490B1 (en) | Process for preparing N-[1-(S)-ethoxycarbonyl-3-phenylpropyl]-L-alanine N-carboxyanhydride | |
| US5679827A (en) | Cyanobenzenesulfenyl halide and process for preparation of 3-substituted benzisothiazole using the same | |
| US4673740A (en) | Preparation of substituted 2-phenyl-4H-3,1-benzoxazin-4-ones | |
| US6040443A (en) | Process for the production of benzoxazinones | |
| JPH07215950A (en) | Production of substituted quinazoline-2,4-dione | |
| CA1063106A (en) | Pharmacologically active pyrrolodiazepines | |
| JP2000169456A (en) | Production of 3-aryldihydro-1,3-benzoxazine compound | |
| GB2262097A (en) | Manufacture of 4H-3,1-benzoxazin-4-ones | |
| US4772747A (en) | Preparation of 2,4,6-trichlorophenylhydrazine | |
| US4203904A (en) | Alkylation of aniline with a lactone in the presence of a base | |
| US5710319A (en) | Process for the preparation of substituted quinazoline-2,4-diones | |
| US5288867A (en) | Process for the preparation of 2-hydroxy-4,6-diaryl-1,3,5-triazines | |
| IL46011A (en) | Production of 3-substituted 1h-2,1,3-benzothiadiazin-4(3h)-one-2,2,-dioxides | |
| US3655664A (en) | 2-aryl-4(3h)-quinazolinones | |
| JPH01203374A (en) | Production of benzothiazepinone derivative | |
| CN1095708A (en) | Azanol ether, their salt and the preparation of intermediate thereof | |
| IL98877A (en) | Process for the preparation of n-alkylsulfonylamino sulfonylureas | |
| EP0208477B1 (en) | Process for producing chlorophenylhydrazine compounds | |
| US5952494A (en) | Method for the preparation of pyrido benzoxazine derivatives | |
| US4269985A (en) | Process for the preparation of 2-amino-5-nitrothiazole | |
| Oskooie et al. | Mild and efficient conversion of oximes into arylhydrazones catalysed by ferric perchlorate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |